CN106082300B - A kind of asymmetric complicated hollow-core construction CeO2Preparation method - Google Patents
A kind of asymmetric complicated hollow-core construction CeO2Preparation method Download PDFInfo
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- CN106082300B CN106082300B CN201610543388.9A CN201610543388A CN106082300B CN 106082300 B CN106082300 B CN 106082300B CN 201610543388 A CN201610543388 A CN 201610543388A CN 106082300 B CN106082300 B CN 106082300B
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- C—CHEMISTRY; METALLURGY
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- C01F17/00—Compounds of rare earth metals
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
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Abstract
The invention discloses the asymmetric complicated hollow-core construction CeO of one kind2Preparation method.First with SiO2Nanosphere prepares SiO as hard template with cerous nitrate and urea reaction2@Ce(OH)CO3Presoma, then passes through and aqueous slkali reaction, acid elution process step, you can obtain CeO2Hollow ball is embedded in CeO2The asymmetric complicated hollow-core construction of nanotube.Compared to existing hollow ball@hollow balls, the complicated hollow-core construction of nanotube@nanotubes symmetry, hollow ball@nanotubes prepared by the present invention are unsymmetric structure, enrich the preparation method of complicated hollow-core construction, and preparation method of the present invention there is green economy, it is simple to operate.
Description
Technical field
The invention belongs to technical field of function materials, specifically, the present invention relates to the asymmetric complicated hollow-core construction of one kind
CeO2Preparation method.
Background technology
Nano hollow structure metal oxide is due to spies such as low-density, high-ratio surface, high osmosis, hollow structures
Point, thus it is widely used in the fields such as catalyst, medicinal slow release agent, gas sensitive, catalysis material, lithium ion battery, each
Plant in metal oxide, cerium oxide is because of its superior oxygen storage capacity and Ce3+/Ce4+Between effective reversible transition the advantages of,
So as to be received much concern in catalytic field.
So far, simple hollow-core construction（Single shell hollow sphere or nanotube）Metal oxide wide coverage.Recently
Research finds that complicated hollow-core construction is due to effectively using inner space, higher material specific surface area is preferably tied
The structural advantages such as structure stability, show the performance more excellent than simple hollow-core construction.For example, double-deck hollow-core construction Au/CeO2
Catalytic performance is better than individual layer hollow-core construction Au/CeO in reduction p-nitrophenol catalytic reaction2（Chemical Science, 5
(2014)：4221–4226）.At present, prepare complicated hollow structure material and mainly use hard template method and soft template method.For example it is special
It is that hard template prepares many shell-layer metal oxide hollow balls that sharp CN201010544562.4, which is reported using carbon ball,.First by metal
Salt is dissolved in carbon ball suspension, passes through modulation metal salt concentrations, the adsorption conditionses such as solution ph, soaking temperature and time, control
Metal salt enters quantity, depth and the gradient distribution of carbon ball, the carbon ball for having adsorbed metal ion is heat-treated, you can obtain
Many shell-layer metal oxide hollow balls；Document Angewandte Chemie-International Edition, 46 (2007)：
Reported in 1489-1492 by the use of surfactant cetyl trimethylammonium bromide as soft template and be prepared for Cu2The many shells of O
Hollow ball；Document Langmuir, 26 (2010)：Reported in 15580-15585 double using the preparation of non-equilibrium heat-treating methods
Shell γ-Fe2O3Nanotube.It is non-flat by being carried out to the electrospun fibers being made up of polyvinylpyrrolidone and ironic citrate
Weighing apparatus heat treatment, obtains the γ-Fe with bivalve layer2O3Nanotube.Although the above method is prepared for the hollow-core construction metal oxygen of complexity
There are problems that in compound, but preparation process high-temperature calcination, prepare it is relative complex, in addition, these hollow-core constructions are golden
Category oxide is all symmetrical many shell hollow spheres or tubular construction, asymmetric hollow-core construction（Such as hollow ball@hollow pipes）Metal is aoxidized
Thing but not yet finds report.
The content of the invention
The problem of complicated hollow-core construction metal oxide is present is prepared for prior art with deficiency, the purpose of the present invention to exist
In a kind of asymmetric complicated hollow-core construction CeO of offer2Preparation method.
The present invention is achieved by the following technical solutions：
A kind of asymmetric complicated hollow-core construction CeO2Preparation method, comprises the following steps：
A, alkaline solution, ethanol and deionized water be well mixed, then add silicon substrate presoma, stirred at 25 DEG C
24 hours, finally make to be washed with deionized, dry, obtain the spherical SiO of size uniformity2Particle；
B, the spherical SiO for obtaining step A2Particle is scattered in the mixed solution of cerium salt and urea, is then transferred into reaction
In kettle, centrifuge, wash, dry after being reacted 24 hours at 80 DEG C, obtain bar-shaped SiO2@Ce(OH)CO3Presoma；
C, the obtained presomas of step B and NaOH solution reacted 1 day, then make to be washed with deionized 1 time, then with
NaOH solution is reacted 2 days, is finally made to be washed with deionized, is dried, obtains CeO2-Ce(OH)CO3Composite；
D, the product for obtaining step C are handled with acid, then made to be washed with deionized, are dried, obtain asymmetric
Complicated hollow-core construction CeO2。
Alkaline solution described in above-mentioned steps A is ammoniacal liquor.
Silicon substrate presoma described in above-mentioned steps A is tetraethyl orthosilicate.
The volume ratio of silicon substrate presoma, basic solvent, deionized water and alcohol solvent described in above-mentioned steps A is（1.65~
3.30）：（0.30~0.60）：（0.53~1.06）：（12.50~25.00）.
Cerium salt described in above-mentioned steps B is Ce (NO3)3Or CeCl3。
Reaction condition described in above-mentioned steps B is at a slow speed（200~400 rpm）Stirring.
The concentration of NaOH described in above-mentioned steps C is 2 ~ 4 mol/L.
Acid described in above-mentioned steps D is lactic acid, dilute HNO3Or dilute HCl.
Beneficial effects of the present invention：The present invention provides a kind of asymmetric complicated hollow-core construction CeO2Preparation method, collection is hard
Template is with sacrificing template in one：Pass through SiO2Ball prepares SiO as hard template2@Ce(OH)CO3Presoma, utilizes its work
To sacrifice template asymmetric complicated hollow-core construction CeO is prepared with NaOH solution progress solid-liquid interface reaction2.The present invention prepares bar
Part is gentle, without high-temperature calcination, surfactant or polymer auxiliary, it is not required that cumbersome preparation process, and enriches
The preparation method of complicated hollow-core construction.
Brief description of the drawings
Fig. 1 is the asymmetric complicated hollow-core construction CeO of the gained of embodiment 12Scanning electron microscope (SEM) photograph and transmission electron microscope picture.
Fig. 1 a-b are the asymmetric complicated hollow-core construction CeO of the gained of embodiment 12Scanning electron microscope (SEM) photograph.
Fig. 1 c-d are the asymmetric complicated hollow-core construction CeO of the gained of embodiment 12Transmission electron microscope picture.
Fig. 2 is the bar-shaped porous C eO of the gained of embodiment 22Transmission electron microscope picture.
Embodiment
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings, so that those skilled in the art can be more
The good understanding present invention, but and it is not so limited the present invention.
Embodiment 1
5.3 ml water, 3 ml concentrated ammonia liquors, 125 ml absolute ethyl alcohols are stirred mixing, 16.5 ml are then quickly added into
Tetraethyl orthosilicate, is stirred 24 hours at 25 DEG C, and last products therefrom makes to be washed with deionized, dried, you can obtain chi
Very little homogeneous spherical SiO2Particle；
Take 1.302 g cerous nitrates to be dissolved in 80 ml water, add 800 mg SiO2, ultrasonic 10 min, then stir and add
It is transferred to after entering 1.080 g urea, 30 min of stirring in reactor, centrifuges, washs, dries after being reacted 24 hours at 80 DEG C,
It can obtain bar-shaped SiO2@Ce(OH)CO3Presoma；
Take 500 mg Ce (OH) CO3-SiO2It is scattered in 30 ml NaOH solutions（3 mol/L）In, it is slowly stirred 24 hours,
Then it washed once using deionized water, place into 30 ml NaOH solutions（3 mol/L）In, it is slowly stirred 2 days, finally uses
Deionized water is washed, dried, you can obtain CeO2-Ce(OH)CO3Composite；
By dried sample dispersion in 10 ml water, ultrasonic 1 min is then slowly added at 20 ml lactic acid
Reason, finally makes to be washed with deionized, dries, you can obtain asymmetric complicated hollow-core construction CeO2。
Embodiment 2
5.3 ml water, 3 ml concentrated ammonia liquors, 125 ml absolute ethyl alcohols are stirred mixing, 16.5 ml are then quickly added into
Tetraethyl orthosilicate, is stirred 24 hours at 25 DEG C, and last products therefrom makes to be washed with deionized, dried, you can obtain chi
Very little homogeneous spherical SiO2Particle；
Take 1.302 g cerous nitrates to be dissolved in 80 ml water, add 800 mg SiO2, ultrasonic 10 min, then stir and add
It is transferred to after entering 1.080 g urea, 30 min of stirring in reactor, centrifuges, washs, dries after being reacted 24 hours at 80 DEG C,
It can obtain bar-shaped SiO2@Ce(OH)CO3Presoma；
Take Ce (OH) CO that 300 mg are prepared3-SiO2Calcined 4 hours at 550 DEG C, heating rate is 5 DEG C/min, so
Afterwards by the sample dispersion after calcining in 30 ml NaOH solution（2 mol/L）In, stirred 2 hours at 80 DEG C, you can obtain rod
Shape porous C eO2。
Embodiment 3
5.3 ml water, 3 ml concentrated ammonia liquors, 125 ml absolute ethyl alcohols are stirred mixing, 16.5 ml are then quickly added into
Tetraethyl orthosilicate, is stirred 24 hours at 25 DEG C, and last products therefrom makes to be washed with deionized, dried, you can obtain chi
Very little homogeneous spherical SiO2Particle；
Take 1.302 g cerous nitrates to be dissolved in 80 ml water, add 800 mg SiO2, ultrasonic 10 min, then stir and add
It is transferred to after entering 1.080 g urea, 30 min of stirring in reactor, centrifuges, washs, dries after being reacted 24 hours at 80 DEG C,
It can obtain bar-shaped SiO2@Ce(OH)CO3Presoma；
Take 500 mg Ce (OH) CO3-SiO2It is scattered in 30 ml NaOH solutions（3 mol/L）In, it is slowly stirred 24 hours,
Then it washed once using deionized water, place into 30 ml NaOH solutions（3 mol/L）In, it is slowly stirred 2 days, finally uses
Deionized water is washed, dried, you can obtain CeO2-Ce(OH)CO3Composite；
By dried sample dispersion in 10 ml water, ultrasonic 1 min is then slowly added into 5 ml dust technologies（1 mol/
L）Handled, finally make to be washed with deionized, dry, you can obtain asymmetric complicated hollow-core construction CeO2。
Embodiment 4
5.3 ml water, 3 ml concentrated ammonia liquors, 125 ml absolute ethyl alcohols are stirred mixing, 16.5 ml are then quickly added into
Tetraethyl orthosilicate, is stirred 24 hours at 25 DEG C, and last products therefrom makes to be washed with deionized, dried, you can obtain chi
Very little homogeneous spherical SiO2Particle；
Take 1.302 g cerous nitrates to be dissolved in 80 ml water, add 800 mg SiO2, ultrasonic 10 min, then stir and add
It is transferred to after entering 1.080 g urea, 30 min of stirring in reactor, centrifuges, washs, dries after being reacted 24 hours at 80 DEG C,
It can obtain bar-shaped SiO2@Ce(OH)CO3Presoma；
Take 500 mg Ce (OH) CO3-SiO2It is scattered in 30 ml NaOH solutions（3 mol/L）In, it is slowly stirred 24 hours,
Then it washed once using deionized water, place into 30 ml NaOH solutions（3 mol/L）In, it is slowly stirred 2 days, finally uses
Deionized water is washed, dried, you can obtain CeO2-Ce(OH)CO3Composite；
By dried sample dispersion in 10 ml water, ultrasonic 1 min is then slowly added into 5 ml watery hydrochloric acid（1 mol/
L）Handled, finally make to be washed with deionized, dry, you can obtain asymmetric complicated hollow-core construction CeO2。
It can be drawn by above-described embodiment 1-2 and with reference to accompanying drawing：In Ce (OH) CO3During nucleating growth, spherical SiO2Grain
Son can effectively be embedded in Ce (OH) CO as hard template3Internal and surface；Work as SiO2@Ce(OH)CO3Reacted with NaOH solution,
The SiO on surface2Can gradually it dissolve；With the extension in reaction time, NaOH solution is spread in Ce (OH) CO3Continue to dissolve in inside
SiO2, form hollow-core construction；Meanwhile, Ce (OH) CO3Sacrifice template is served as, it is anti-to occur slow solid-liquid interface with NaOH solution
Should, generate CeO2.As Ce (OH) CO of residual3After acid dissolving, CeO just can be obtained2Hollow ball is embedded in CeO2Nanotube it is non-
Symmetrical complexity hollow-core construction.
Claims (4)
1. a kind of asymmetric complicated hollow-core construction CeO2Preparation method, it is characterised in that methods described comprises the following steps：
A, ammoniacal liquor, ethanol and deionized water be well mixed, then add tetraethyl orthosilicate, 24 are stirred at 25 DEG C small
When, finally make to be washed with deionized, dry, obtain the spherical SiO of size uniformity2Particle；
B, the spherical SiO for obtaining step A2Particle is scattered in the mixed solution of cerous nitrate and urea, is then transferred into reactor
In, centrifuge, wash, dry after being reacted 24 hours at 80 DEG C, obtain bar-shaped SiO2@Ce(OH)CO3Presoma；
C, the obtained presomas of step B and NaOH solution reacted 1 day, then make to be washed with deionized 1 time, then it is molten with NaOH
Liquid reacts 2 days, finally makes to be washed with deionized, dries, obtains CeO2-Ce(OH)CO3Composite；
D, the product for obtaining step C are handled with acid, then made to be washed with deionized, are dried, obtain hollow ball and inlay
In the CeO of the asymmetric complicated hollow-core construction of nanotube2。
2. the asymmetric complicated hollow-core construction CeO of one kind according to claim 12Preparation method, it is characterised in that：It is described
The volume ratio of silicon substrate presoma, basic solvent, deionized water and alcohol solvent described in step A is（1.65~3.30）：（0.30~
0.60）：（0.53~1.06）：（12.50~25.00）.
3. the asymmetric complicated hollow-core construction CeO of one kind according to claim 12Preparation method, it is characterised in that：It is described
The concentration of NaOH described in step C is 2 ~ 4 mol/L.
4. the asymmetric complicated hollow-core construction CeO of one kind according to claim 12Preparation method, it is characterised in that：It is described
Acid described in step D is lactic acid, dilute HNO3Or dilute HCl.
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